CN1962477A - Process for catalyzing oxidation of organic compounds by ultraviolet - Google Patents

Process for catalyzing oxidation of organic compounds by ultraviolet Download PDF

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Publication number
CN1962477A
CN1962477A CN 200610117583 CN200610117583A CN1962477A CN 1962477 A CN1962477 A CN 1962477A CN 200610117583 CN200610117583 CN 200610117583 CN 200610117583 A CN200610117583 A CN 200610117583A CN 1962477 A CN1962477 A CN 1962477A
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ultraviolet
organic compounds
phosphate
nano
catalyzing oxidation
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CN100415661C (en
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周保学
金竹静
朱新远
李龙海
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

The invention discloses a photoelectric catalytic oxidizing method of organics through ultraviolet, which comprises the following steps: adopting nanometer TiO2 film as optical anode; setting Ag/AgCl as reference electrode; making Pt as opposite electrode in the battery system; adopting the density of phosphor element at 0.1-2.8mol/l phosphate or phosphate buffer as electrolyte; proceeding ultraviolet photoelectric catalytic oxidizing reaction for organics, wherein the phosphate is one of orthophosphates, monohydric phosphate and dihydrogenphosphate or their buffer solution.

Description

The method of catalyzing oxidation of organic compounds by ultraviolet
Technical field
The present invention relates to a kind of method of catalyzing oxidation of organic compounds by ultraviolet, especially related to a kind of method of utilizing phosphoric acid salt or phosphate buffered saline buffer as electrolytical catalyzing oxidation of organic compounds by ultraviolet.Belong to the photoelectrocatalysis technical field.
Background technology
The photoelectrocatalysis technology is a kind of novel high-level oxidation technology, it utilizes the photoelectric-synergetic effect, improve the photochemical catalytic oxidation ability, by applying certain bias-voltage at the light anode, impel light induced electron to migrate to external circuit, suppress light induced electron and hole-recombination, strengthen the hole organic oxidation capacity in the water body.Utilize the organic substance in this method oxidized waste water, cause people's attention.The factor that influences catalyzing oxidation of organic compounds is a lot, comprises electrode materials, bias-voltage, ionogen, temperature of reaction, light source, matter property and concentration etc.In recent years with TiO 2The semiconductor optical anode electrode materials is the method for the catalyzing oxidation of organic compounds by ultraviolet of representative, because its oxidation capacity is strong, and has caused people's very big concern.In the reaction of catalyzing oxidation of organic compounds by ultraviolet, ionogen needs good electrical conductivity, diffustivity, stability, light transmission etc., and electrolytical performance impact the efficient of catalyzing oxidation of organic compounds.But in the method for existing catalyzing oxidation of organic compounds by ultraviolet, the ionogen of employing mainly is nitrate and sulfate liquor, and they all have its limitation in the reaction of catalyzing oxidation of organic compounds by ultraviolet, has influenced the photoelectrocatalysis efficient of this method.As people such as Australian Zhao Huijun (Shanqing Zhang, Huijun Zhao, Dianlu Jiang, etal., Analytica Chimica Acta[J], 2004,514 (2): 89～97; Huijun Zhao, Dianlu Jiang, Shanqing Zhang, et al.Anal.Chem.[J], and people (Cheng Cangcang etc. such as Cheng Cangcang 2004,76:155～160),, China Environmental Science 2005,25 (3): 380～384) just adopted SODIUMNITRATE and metabisulfite solution ionogen as the reaction of UV-light photoelectrocatalysis.Although nitrate is as the ionogen of catalyzing oxidation of organic compounds reaction, have that diffustivity is good, good conductivity, electrode stability be good, but nitrate is for the very strong sorption of UV-light, can reduce the irradiance of UV-light, and then reduce the efficient of catalyzing oxidation of organic compounds by ultraviolet reaction.Vitriol is as the ionogen in the photoelectrocatalysis reaction, although do not absorb in the ultraviolet region, and electrode stability is good, and its solubleness is less, and especially saturation solubility is less under the winter low temperature, and easily crystallization also can influence UV-light photoelectrocatalysis reaction efficiency.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method of utilizing phosphoric acid salt or phosphate buffered saline buffer as electrolytical catalyzing oxidation of organic compounds by ultraviolet is provided, good, the easy diffusion of this ionogen light transmission, good conductivity, electrode stability is good and solubleness is big, can improve the efficient of catalyzing oxidation of organic compounds method.
Concrete grammar of the present invention is: with nano-TiO 2Film is the light anode, and Ag/AgCl is a reference electrode, and Pt is in the battery system of counter electrode, and the concentration that adopts phosphoric P is that phosphoric acid salt or the phosphate buffered saline buffer of 0.1～2.8mol/l is ionogen, carries out the reaction of catalyzing oxidation of organic compounds by ultraviolet.
Phosphoric acid salt of the present invention is phosphoric acid normal salt, monohydric phosphate or dihydrogen phosphate.
Phosphate buffered saline buffer of the present invention is the buffered soln that is made of phosphoric acid normal salt, monohydric phosphate or dihydrogen phosphate.
Nano-TiO of the present invention 2The film light anode can be by the nano-TiO of prior art in the conductive glass surface preparation 2Film also can be the TiO by the anode oxidation method preparation 2Nano-pipe array thin film.
The method of catalyzing oxidation of organic compounds by ultraviolet of the present invention can be applied in the reactions such as photoelectric catalysis degrading organic waste water and photoelectrocatalysis mensuration chemical oxygen demand (COD).
The present invention compared with the prior art advantage is:
1, the absorption of the ionogen UV-light of method use of the present invention is few, and light transmission is good, and is low to the effect that the energy of UV-light is subdued, and therefore compares with using the electrolytical method of SODIUMNITRATE, and speed of reaction is very fast, and the time is short;
2, the electrolytic conductivity height that uses of method of the present invention, electrode stability is good, and the solubleness height, and easily diffusion also is easy to dissolving under cold condition, and the solution of configurable high density helps improving the efficient of catalyzing oxidation of organic compounds by ultraviolet method.
Description of drawings
Fig. 1 is a nano-TiO 2Powder and 3 kinds of electrolytical ultraviolet-visible absorption spectroscopies.
Among Fig. 1,1,2.0mol/L NaNO 32, P25 nano-TiO 23,2.0mol/L NaH 2PO 44,2.0mol/L KCl.
Fig. 2 is for adopting NaNO 3And NaH 2PO 4Make the I～t curve of electrolytical UV-light photoelectrocatalysioxidization oxidization glucose method.
Among Fig. 2,5, adopt NaNO 3For COD value in the electrolytical method is 45mg/LO 2Glucose degradation I～t curve; 6, adopt NaH 2PO 4For COD value in the electrolytical method is 45mg/LO 2Glucose degradation I～t curve.
Fig. 3 is the 3 kinds of electrolytical UV-light photoelectrocatalysis I of difference～t baselines
Among Fig. 3,7, NaNO 38, NaH 2PO 49, KCl.
Embodiment
Below by embodiment technical scheme of the present invention is described further, following embodiment does not constitute technical scheme of the present invention and limits.
Embodiment 1:
With nano-TiO in the conductive glass surface preparation 2Film is the light anode, and Ag/AgCl is a reference electrode, and Pt is in the three-electrode battery of counter electrode, is the NaH of 0.1mol/L with phosphoric concentration 2PO 4Solution is ionogen, is 45mg/LO to the COD value 2Glucose solution degrade, its degradation rate is 25.4 microcoulombs electric weight/second.
Embodiment 2:
With nano-TiO in the conductive glass surface preparation 2Film is the light anode, and Ag/AgCl is a reference electrode, and Pt is in the three-electrode battery of counter electrode, is the NaH of 2.0mol/L with phosphoric concentration 2PO 4Solution is ionogen, is 45mg/LO to the COD value 2Glucose solution degrade, its degradation rate is 96.4 microcoulombs electric weight/second.
Among Fig. 13 is 2.0mol/L NaH 2PO 4Solution ultraviolet-visible absorption spectroscopy, 1 among Fig. 1 are 2.0mol/L NaNO 3The solution ultraviolet-visible absorption spectroscopy, as seen from Figure 1, NaH 2PO 4Solution and NaNO 3Solution is compared, NaH 2PO 4Solution absorbs low in the ultraviolet region, light transmission is good.Among Fig. 38 is for adopting NaH 2PO 4Be electrolytical UV-light photoelectrocatalysis I～t baseline, 9 among Fig. 3 is electrolytical UV-light photoelectrocatalysis I～t baseline for adopting KCl, as seen from Figure 3, with the KCl electrolytic condenser, adopt NaH 2PO 4Be the electrolyte-electrode good stability.
Embodiment 3:
With nano-TiO in the conductive glass surface preparation 2Film is the light anode, and Ag/AgCl is a reference electrode, and Pt is in the three-electrode battery of counter electrode, is the NaH of 2.8mol/L with phosphoric concentration 2PO 4Solution is ionogen, is 45mg/LO to the COD value 2Glucose solution degrade, its degradation rate is 92.1 microcoulombs electric weight/second.
Embodiment 4:(reference examples)
With nano-TiO in the conductive glass surface preparation 2Film is the light anode, and Ag/AgCl is a reference electrode, and Pt is in the three-electrode battery of counter electrode, with the NaNO of 2.0mol/L 3Solution is ionogen, is 45mg/LO to the COD value 2Glucose solution degrade, its degradation rate is 73.1 microcoulombs electric weight/second.
Among Fig. 25 is for adopting NaNO 3Be glucose degradation I～t curve in the electrolytical method, 6 among Fig. 2 is for adopting NaH 2PO 4Be glucose degradation I～t curve in the electrolytical method, as seen from Figure 2, the organism of the COD of the same concentration of degrading adopts NaH 2PO 4Very fast for electrolytical method speed of reaction, the used time is short.
Embodiment 5:(reference examples)
With nano-TiO in the conductive glass surface preparation 2Film is the light anode, and Ag/AgCl is a reference electrode, and Pt is in the three-electrode battery of counter electrode, with the Na of 1mol/L 2SO 4Solution is ionogen, is 45mg/LO to the COD value 2Glucose solution degrade, its degradation rate is 56.4 microcoulombs electric weight/second.
Embodiment 6:
With nano-TiO in the conductive glass surface preparation 2Film is the light anode, and Ag/AgCl is a reference electrode, and Pt is in the three-electrode battery of counter electrode, is 0.2mol/l H with phosphoric concentration 3PO 4/ NaH 2PO 4Damping fluid is 200mg/LO as ionogen to the COD value 2Printing and dyeing organic waste water degrade, its degradation rate is 65.3 microcoulombs electric weight/second.
Embodiment 7:
With TiO 2Nano-pipe array thin film is the light anode, and Ag/AgCl is a reference electrode, and Pt is in the three-electrode battery of counter electrode, is 0.2mol/l NaHPO with phosphoric concentration 4/ NaH 2PO 4Damping fluid is 50mg/LO as ionogen to the COD value 2The dihydroxyphenyl propane organic wastewater 5min that degrades, the COD clearance is more than 90%.
Embodiment 8:
The nano-TiO that obtains through sputtering method with conductive glass surface 2Film is the light anode, and Ag/AgCl is a reference electrode, and Pt is in the three-electrode battery of counter electrode, is 0.5mol/l Na with phosphoric concentration 3PO 4/ NaHPO 4Damping fluid is degraded to the organic waste water that is mixed with of COD value 500mg/l as the ionogen of photoelectrocatalysis reaction, and the COD clearance is more than 70% behind the 30min.

Claims (4)

1, a kind of method of catalyzing oxidation of organic compounds by ultraviolet is characterized in that: with nano-TiO 2Film is the light anode, and Ag/AgCl is a reference electrode, and Pt is in the battery system of counter electrode, and employing phosphoric concentration is that phosphoric acid salt or the phosphate buffered saline buffer of 0.1～2.8mol/l is ionogen, carries out the reaction of catalyzing oxidation of organic compounds by ultraviolet.
2, according to the method for the catalyzing oxidation of organic compounds by ultraviolet of claim 1, it is characterized in that described phosphoric acid salt is phosphoric acid normal salt, monohydric phosphate or dihydrogen phosphate.
3, according to the method for the catalyzing oxidation of organic compounds by ultraviolet of claim 1, it is characterized in that described phosphate buffered saline buffer is the buffered soln that is made of phosphoric acid normal salt, monohydric phosphate or dihydrogen phosphate.
4, according to the method for the catalyzing oxidation of organic compounds by ultraviolet of claim 1, it is characterized in that described smooth anode is a nano-TiO 2Film, or TiO2 nano-pipe array thin film.
CNB2006101175831A 2006-10-26 2006-10-26 Process for catalyzing oxidation of organic compounds by ultraviolet Expired - Fee Related CN100415661C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219279A (en) * 2011-04-13 2011-10-19 同济大学 Visible light catalytic degradation method of organic pollutants based on TiO2/carbon aerogel electrode
CN104085975A (en) * 2014-06-23 2014-10-08 陕西师范大学 Method for degrading sulfadimethoxine under catalysis of chloroperoxidase
CN114318374A (en) * 2022-01-06 2022-04-12 大连工业大学 Method for degrading hyaluronic acid based on titanium dioxide modified ITO electrode photoelectrocatalysis

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007516577A (en) * 2003-05-30 2007-06-21 ザ アリゾナ ボード オブ リージェンツ アクティング オン ビハーフ オブ アリゾナ ステート ユニバーシティ Use of photobiofuel cells in the production of hydrogen and other substances

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219279A (en) * 2011-04-13 2011-10-19 同济大学 Visible light catalytic degradation method of organic pollutants based on TiO2/carbon aerogel electrode
CN104085975A (en) * 2014-06-23 2014-10-08 陕西师范大学 Method for degrading sulfadimethoxine under catalysis of chloroperoxidase
CN104085975B (en) * 2014-06-23 2016-05-04 陕西师范大学 The method of chloroperoxidase catalytic degradation sulfadimethoxine
CN114318374A (en) * 2022-01-06 2022-04-12 大连工业大学 Method for degrading hyaluronic acid based on titanium dioxide modified ITO electrode photoelectrocatalysis

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